Structure evolution of soft magnetic (Fe36Co36B19.2Si4.8Nb4)100−xCux (x=0 and 0.5) bulk glassy alloys

AbstractFully amorphous rods with diameters up to 2mm diameter were obtained upon 0.5at.% Cu addition to the Fe36Co36B19.2Si4.8Nb4 bulk metallic glass. The Cu-added glass shows a very good thermal stability but, in comparison with the Cu-free base alloy, the entire crystallization behavior is drastically changed. Upon heating, the glassy (Fe36Co36B19.2Si4.8Nb4)99.5Cu0.5 samples show two glass transitions-like events, separated by an interval of more than 100K, in between which a bcc-(Fe,Co) solid solution is formed. The soft magnetic properties are preserved upon Cu-addition and the samples show a saturation magnetization of 1.1T combined with less than 2A/m coercivity. The relaxation behavior prior to crystallization, as well as the crystallization behavior, were studied by time-resolved X-ray diffraction using synchrotron radiation. It was found that both glassy alloys behave similar at temperatures below the glass transition. Irreversible structural transformations take place when approaching the glass transition and in the supercooled liquid region

Operando X-ray absorption tomography for the characterization of lithium metal electrode morphology and heterogeneity in a liquid Li/S cell

International audienceLithium/sulfur batteries have been under intense study for the last two decades, due to the high specific capacity promised by elemental sulfur as an active material. Sulfur is also cheap, abundant and non-toxic compared to conventional transition metal oxides. The Li/S electrochemical cell is traditionally composed of a sulfur-based electrode, an organic liquid electrolyte and a lithium metal electrode. Lithium metal technologies have received a renewed interest, due to the light weight and low operating voltage of the lithium electrode, which makes it the ultimate choice to be combined with high-energy positive electrode materials. In this paper, operando X-ray absorption and phase contrast tomography were employed to characterize the lithium metal electrode morphology and heterogeneity in a liquid Li/S cell. It was observed that oxidation of the lithium foil occurs in a heterogeneous fashion with pit formation from the beginning of discharge, with the pits growing in diameter, depth and quantity during the discharge. Using Faraday’s law, the local current density distribution was calculated to confirm the strongly heterogeneous behavior of the lithium metal electrode. We demonstrate that decreasing the current density leads to lithium stripping/plating occurring more homogenously, with the formation of a smaller number of pits

Operando investigation of the lithium/sulfur battery system by coupled X-ray absorption tomography and X-ray diffraction computed tomography

International audienceHigh capacity sulfur electrodes are expected to be used in the next-generation of high energy density and low cost rechargeable lithium batteries. The positive sulfur electrode undergoes complex electrochemical reactions, which cause morphological changes of the composite electrode while cycling. In the course to deeper understand the failures of this rather complex, but promising technology, the operando technics are in the heart of the advanced characterizations. In this study, a new electrochemical cell was designed which allows, for the first time, the combination operando of multimodal X-ray characterizations: the absorption tomography to study the morphological evolution of electrodes, and the X-ray diffraction computed tomography to probe locally the structural modification of the crystalline active materials S 8 and Li 2 S. The combination of these two techniques simultaneously with the electrochemical cycling, allows the production of correlated 3D-maps of quantitative phase distributions and morphology in the electrode, with time resolution on the scale of battery kinetics. It was thus possible to show the heterogeneous behavior in the bulk of the electrode and to propose kinetics la

Synthesis, crystallization, X-ray structural characterization and solid-state assembly of a cyclic hexapeptoid with propargyl and methoxyethyl side chains

The synthesis and the structural characterization of a cyclic hexapeptoid with four methoxyethyl and two propargyl side chains have disclosed the presence of a hydrate crystal form [form (I)] and an anhydrous crystal form [form (II)]. The relative amounts of form (I) and form (II) in the as-purified product were determined by Rietveld refinement and depend on the purification procedures. In crystal form (I), peptoid molecules assemble in a columnar arrangement by means of side-chain-to-backbone C CH OC hydrogen bonds. In the anhydrous crystal form (II), cyclopeptoid molecules form ribbons by means of backbone-to-backbone CH2 OC hydrogen bonds, thus mimicking -sheet secondary structures in proteins. In both crystal forms side chains act as joints among the columns or the ribbons and contribute to the stability of the whole solid-state assembly. Water molecules in the hydrate crystal form (I) bridge columns of cyclic peptoid molecules, providing a more efficient packing

Location and characterization of heterogeneous phases within Mary Rose wood

Preserving the Mary Rose oak hull for future generations is a major challenge due to the highly heterogeneous nature of waterlogged wooden artifacts, which contain polycrystalline, amorphous, and nanostructured materials that test traditional characterization methods. Effective conservation requires detailed knowledge of the distribution and chemical nature of these species to develop strategies for preventing multiple chemo-mechanical degradation pathways. Here, we apply synchrotron-based computed tomography total scattering methods to the Mary Rose keelson wood that provides valuable position-resolved structural information on multiple embedded species of different length and concentration scales. We identify 5 nm zinc sulfide nanoparticles in the wood, presumably deposits from bacteria operating on the sulfur energy cycle under the anaerobic conditions on the seabed. These are identified as precursors to acid attack on the wood upon removal to an aerobic environment. These insights inform not only next-generation conservation strategies, but also the efficacy and unforeseen issues of previous treatments

Destabilizing high-capacity high entropy hydrides via earth abundant substitutions: from predictions to experimental validation

The vast chemical space of high entropy alloys (HEAs) makes trial-and-error experimental approaches for materials discovery intractable and often necessitates data-driven and/or first principles computational insights to successfully target materials with desired properties. In the context of materials discovery for hydrogen storage applications, a theoretical prediction-experimental validation approach can vastly accelerate the search for substitution strategies to destabilize high-capacity hydrides based on benchmark HEAs, e.g. TiVNbCr alloys. Here, machine learning predictions, corroborated by density functional theory calculations, predict substantial hydride destabilization with increasing substitution of earth-abundant Fe content in the (TiVNb)75Cr25-xFex system. The as-prepared alloys crystallize in a single-phase bcc lattice for limited Fe content x < 7, while larger Fe content favors the formation of a secondary C14 Laves phase intermetallic. Short range order for alloys with x < 7 can be well described by a random distribution of atoms within the bcc lattice without lattice distortion. Hydrogen absorption experiments performed on selected alloys validate the predicted thermodynamic destabilization of the corresponding fcc hydrides and demonstrate promising lifecycle performance through reversible absorption/desorption. This demonstrates the potential of computationally expedited hydride discovery and points to further opportunities for optimizing bcc alloy ↔ fcc hydrides for practical hydrogen storage applications

Tetracarbonates in silicate melts may be at the origin of a deep carbon reservoir in the deep Earth

Much of Earth’s carbon may have been stripped away from the silicate mantle by dense metallic-iron during core formation. However, at deep magma ocean conditions carbon becomes less siderophile and thus large amounts of it may be stranded instead in the deep mantle. Here, we describe the structure and compaction mechanisms of carbonate glass to deep mantle pressures. Our results, based on non-resonant inelastic X-ray scattering, X-ray diffraction and ab initio calculations, demonstrate a pressure-induced change in hybridization of carbon from sp2 to sp3 starting at 40 GPa, due to the conversion of [3]CO32- groups into [4]CO44- units, which is completed at ~112 GPa. The pressure-induced change of carbon coordination number from three to four increases possibilities for carbon-oxygen interactions with lower mantle silicate melts. sp3 hybridized carbon provides a mechanism for changing the presumed siderophile nature of deep carbon, becoming a possible source for carbon-rich emissions registered at the surface in intra-plate and near-ridge hot spots.ISSN:2662-443